Altering raspberry flavored foodstuffs with 4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butanol and/or 4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-2-butanol, and/or acetates thereof

ABSTRACT

Methods for preparing foodstuffs, flavoring compositions for foodstuffs, perfume compositions and ingredients for perfume compositions by including therein 4-(2,6,6-trimethyl-1,3cyclohexadien-1-yl)-2-butanol or 4-(6,6-dimethyl-2-methylene-3cyclohexen-1-yl)-2-butanol or acetates thereof to produce: A. In food flavorings, green, violet, floral, woody, leathery, piney flavor notes and violet, green, floral, woody, piney aroma notes for improving the taste and aroma of artificial raspberry flavoring compositions; and B. In perfumes, a leathery, green, orris, seashore, mimosa, clary sage, woody, fruity, ionone character with a slight musky nuance AS WELL AS THE FOODSTUFF FLAVORING COMPOSITIONS AND PERFUME COMPOSITIONS CONTAINING 4-(2,6,6-TRIMETHYL-1,3-CYCLOHEXADIEN-1YL)-2-BUTANOL AND/OR 4-(6,6-DIMETHYL-2-METHYLENE-3-CYCLOHEXEN-1YL)-2-BUTANOL AND/OR 4-(2,6,6-TRIMETHYL-1,3-CYCLOHEXADIEN-1-YL)2-BUTYL ACETATE AND/OR 4-(6,6-DIMETHYL-2-METHYLENE-3-CYCLOHEXEN1-YL)-2-BUTYL ACETATE, AND IN ADDITION, THE NOVEL COMPOUNDS 4(2,6,6-TRIMETHYL-1,3-CYCLOHEXADIEN-1-YL)-2-BUTANOL AND 4-(6,6DIMETHYL-2-METHYLENE-3-CYCLOHEXEN-1-YL)-2-BUTANOL, AND PROCESSES FOR PREPARING THE AFOREMENTIONED ALCOHOLS AND ACETATE ESTERS THEREOF.

[22] Filed:

[21] Appl.No.:46l,704

Mookherjee et a].

[4 1 Aug. 12, 1975 ALTERING RASPBERRY FLAVORED FOODSTUFFS WITH 4-(2,6,6-TRIMETHYL- l ,3- CYCLOHEXADIEN- 1-YL)-2-BUTANOL AND/OR 4-( 6,6-DIMETHYL-2-METHYLENE-3- CYCLOHEXEN- l-YL)-2-BUTANOL, AND/OR ACETATESTHEREOF [75] Inventors: Braja Dulal Mookherjee, Matawan;

Manfred Hugo Vock, Locust, both of N.J.; Carlos Benaim, Hartsdale;Edward J. Shuster, Brooklyn, both of NY.

[73] Assignee: International Flavors & Fragrances Inc., New York, NY.

Apr. 17, 1974 [52] US. Cl 426/538; 260/586 R; 260/617 A; 260/488 R;252/522 [51] Int. Cl. A23L 1/226; A231. 1/235 [58] Field of Search260/586 R, 617 R, 488 R, 260/488 A, 617 A, 617 B; 426/65, 175

3/1959 Kaiser et a1..... 12/1965 Winter 426/65 OTHER PUBLICATIONSFenarolis Handbook of Flavor Ingredients, 1971, Ed-

ited by Furia et al., Chemical Rubber, Cleveland, pp.

442, 666-670. Kruk and DeBoer, Recueil, Vol. 87, 641-654.

[ 5 7] ABSTRACT Methods for preparing foodstuffs, flavoring compositionsfor foodstuffs, perfume compositions and ingredients for perfumecompositions by including therein 4-( 2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butanol or4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-2- butanol or acetatesthereof to produce:

a. In food flavorings, green, violet, floral, woody, leathery, pineyflavor notes and violet, green, floral, woody, piney aroma notes forimproving the taste and aroma of artificial raspberry flavoringcompositions; and

b. In perfumes, a leathery, green, orris, seashore,

mimosa, clary sage, woody, fruity, character with a slight musky nuanceas well as the foodstuff flavoring compositions and perfume compositionscontaining 4-(2,6,6-trimethyl- 1,3-cyclohexadien-l-yl)-2-butanol and/or4-(6,6- dimethyl-2-methylene-3-cyclohexenl-yl )-2-butanol and/or4-(2,6,6-trimethyl- 1 ,3-cyclohexadien- 1-yl)-2- butyl acetate and/or4-(6,6-dimethyl-2-methylene-3- cyclohexen-l-y1)-2-butyl acetate, and inaddition, the novel compounds 4-( 2,6,6-trimethyl-1 ,3-cyclohexadien-l-yl)-2-butanol and 4-(6,6-dimethyl-2-methylene-3-cyclohexenl-yl )-2-butanol, and processes for preparing theaforementioned alcohols and acetate esters thereof.

9 Claims, N0 Drawings ionone ALTERING RASPBERRY FLAVORED FOODSTUFFS WITH4-(2,6,6-TRIMETHYL-1,3-CYCLOHEXADIEN-1- YL)-2-BUTANOL AND/OR4-(6,6-DIMETHYL-2-METHYLENE-3- CYCLOHEXEN-l-YL)-2-BUTANOL, AND/ORACETATES THEREOF BACKGROUND OF THE INVENTION ing to substances which canbe used to impart (or enhance) flavors to (or in) various consumablematerials. These substances are used to diminish natural materials someof which may be in short supply and provide more uniform properties infinished products. Violet, green, floral, woody and piney aroma notesare particularly desirable for many uses in fruit flavoring compositionsand consumable articles, e.g., foodstuffs. Leathery, green, orris,seashore, mimosa, clary sage, woody, fruity, ionone and musky aromas areparticularly desirable in perfume compositions.

The flavor and fragrance material having the structure:

'is disclosed in British Pat. No. 1,305,621 issued on Feb.

4-(2,6,6-trimethy1-1,3-cyclohexadien-l yl)-2- butanone having thestructure:

may be synthesized according to the technique of Wolf and Zink, Volume56, Helvetical Chimica Acta., Fasc 3 (1973) pp. 1062-1066, or accordingto Examples I and II of Rowland, US. Pat. No. 3,436,421 issued on April1,1969 by means of bromination of -dihydroionone followed bydebromination. 4-(6,6-dimethyl2- methylene-3-cyclohexen- 1 -yl)-2-butanone having the structure:

is also produced in this process as a bi-product thereof (B.P. 65C at0.15 mm Hg. pressure). 4-(2,6,6- trimethyl-l ,3-cyclohexadienl-yl)-2-butanone is also shown to be a bi-product in the cyclization ofionone to beta ionone by Kruk and De Boer in Volume 87 Recueil 1968) pp.641-654 as an intermediate in preparing other perfumery compounds. Thecompound having the structure:

is disclosed in Japanese Pat. No. 7121 ,015 (Sakan and Isoe)issued June14, 1971.

Japanese Pat. No. 7404,391 discloses a synthesis of the compound havingthe structure:

from a compound having the structure:

This patent indicates that the synthesized compound can improve thearoma and quality of distilled spirits.

are indicated to be intermediates in the synthesis gamma-dihydroiononeby Stoll, Helv. Chim. Acta, 38, 1587 (1955) and British Pat. No.794,416. The synthesis of the compound having the structure:

is disclosed by Naves and Bachmann, Helv. Chim. Acta, 26, 2151 (1943).

Sato and Mashima, Tetrahedron Letters No. 22, Page 1803 (1969) disclosesthe syntheseis of theaspirone from the material having the structure:

but no odor qualities of this acetate are set forth therein. Demole etal., Helv. Chim. Acta, 53, 541 1970) discloses the synthesis of the.alcohol having the structure:

wherein R is acetyl or hydrogen and wherein one of the dashed linesrepresents a carbon-carbon double bond, and the other dashed linerepresents a carbon-carbon single bond. Thus, the 4-(2,6,6-trimethyl-l,3- cyclohexadien- 1 -yl)-2-butanol and/or 4-(6,6-dimethyl-2-methylene-3-cyclohexenl -yl)-2-butanol and/or acetates thereof of ourinvention are capable of supplying and/or potentiating certain flavorand aroma notes usually lacking in many red-berry type flavors as wellas notes usually lacking in many perfumery materials, e.g., orris andclary sage.

The 4-( 2,6,6-trimethyl-l ,3-cyclohexadienl -yl)-2- butanol and/ or 4-(6 ,6-dimethyl-2-methylene-3- cyclohexen-l-yl)-2-butanol and/or acetatesthereof may be prepared by first forming dihydro-a-ionol fromdihydro-a-ionone according to the following Heat Dletnyl ether Thereaction is preferably carried out in an inert solvent such as diethylether at reflux temperatures, e.g., the boiling point of the solvent atatmospheric pressure.

The dihydro-oz-ionol is then esterified via normal esterificationprocedures according to the following reaction: 1

to form the acetate which is, in turn, dehydrogenated, using quinoline,preferably in an inert solvent such as chloroform, at temperatures ofthe order of 5C up to +C at atmospheric pressure, according to thefollowing reaction:

Al a The resulting product, consisting of 70-90% cyclohexadienederivative and 30-10% of methylene cyclohexene derivative may be used asa flavor or perfumery ingredient, as-is" or it may be separated (e.g.,using gasliquid chromatography techniques) or it may be saponified tothe corresponding alcohol mixture using standard saponificationtechniques thus:

The saponification is carried using a base (e.g., KOH or NaOH)preferably in an alcohol solvent medium (e.g., ethanol) at ambientconditions (although temperatues of 50-60C will cause the saponificationreaction to process more rapidly).

The resulting product, consisting of -90% cyclohexadiene derivative and30-10% of methylene cyclohexene derivative may be used as a flavor orperfumery ingredient as-is or it may be separated (e.g., usinggas-liquid chromatography techniques).

When the 4-(2,6,6-trimethyl-1,3-cyclohexadien-lyl)-2-butan0l and/0r4-(6,6-dimethyl-2-methylene-3- cyclohexen-l-yl)-2-butan0l and/0racetates thereof of our invention is used as a food flavor adjuvant thenature of the co-ingredients included with the said 4-(2,6,6-trimethyl-l ,3-cyclohexadienl -yl )-2-butanol and/or4-(6,6-dimethyl-2-methylene-3-cyclohexenlyl)-2-butanol and/or acetatesthereof in formulating the product composition will also serve to alterthe organoleptic characteristics of the ultimate foodstuffs treatedtherewith. As used herein in regard to flavors, the term alter in itsvarious forms means supplying or imparting flavor character or note tootherwise bland, relatively tasteless substance or augmenting theexisting flavor characteristic where a natural flavor is deficient insome regard or supplementing the existing flavor impression to modifyits quality, character or taste. As used herein, the term foodstuffincludes both solid and liquid ingestible materials which usually do butneed not have nutritional value. Thus, foodstuffs include meats,gravies, soups, convenience foods, beverages, dairy products, candies,vegetables, cereals, soft drinks, snacks and the like.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use being extensivelydescribed in the relevant literature. Apart from the requirement thatany such material be ingestibly acceptable and thus non-toxic orotherwise non-deleterious nothing particularly critical resides inselection thereof. Accordingly, such materials which may in general becharacterized as flavoring 'adjuvants or vehicles comprise broadlystabilizers,

thickeners, surface active agents, conditioners, other flavorants andflavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride,antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxyanisole (mixture of 2 and 3 tertiarybutyl-4-hydroxyanisole), butylated hydroxy toluene(2,6di-tertiarybutyl-4- methyl phenol), propyl gallate and the like, andsequestrants, e.g., citric acid.

Thickener compounds include carriers, binders protective colloids,suspending agents, emulsifiers, and the like, e.g., agaragar;carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose amd methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatine, proteinaceous materials; lipids;carbohydrates; starches pectins, and emulsifiers, e.g., mono-anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g., sucrose, corn syrup solids and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono-and diglycerides of fatty acids, lecithin, defoaming andflavordispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phos phate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, turmeric and curcumin and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers; anti-caking agents, e.g., aluminumcalcium'sulfate and tribasic: calcium phosphate; en-

zymes; yeast foods, e.g., calcium lactate and calcium sulfate; nutrientsupplements, e.g., iron salts such as ferric phosphate, ferrousgluconate and the like, riboflavin, vitamins, zinc sources such as zincchloride, zinc sulfate and the like.

Other flavorants and flavor intensifiers include orgnaic acid, e.g.,fatty saturated acids, unsaturated acids and amino acids; alcohols,e.g., primary and secondary alcohols; esters; carbonyl compounds, e.g.,aldehydes and ketones as well as lactones; cyclic organic materialsincluding benzene derivatives; isocyclics, heterocyclics such as furansparticularly 2,5-dimethyl3-acetyl furan and 2-methyl-2,3-dihydrofuran-3-one, pyridines, pyrazines (particularly monoalkyl, dialkyl,trialkyl and tetra-alkyl substituted pyrazines) and the like,sulfurcontaining materials including thiazoles, disulfides, thiols,sulfides, aldehydes, (for example, 3-phenyl-4- pentenal,3-phenyl-3-pentenal, 3-phenyl2-pentenal, 2-phenyl-2-pentenal and-2-phenyl-3-methyl-2- butenal); disulfides and the like; other flavorpotentiators such as monosodium glutamate, guanylates, inosinates,natural and synthetic flavorants such as vanillin, ethyl vanillin,diacetyl, phenethyl-Z-furoate, maltol, natural gums and the like;spices, herbs, essential oils and extractives including bitternessprinciples such as theobromin, caffein, naringin and other suitablematerials creating a bitter effect.

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., foodstuff, whether simulated or natural, and should, in any event,be capable of providing an environment in which the 4-(2,6,6-trimethyll,3-cyclohexadienl -yl)-2-butanol and/or4-(6,6-dimethyl-2-methylene-3-cyclohexen-lyl)-2-butanol and/or acetatesthereof can be dispersed or admixed to provide a homogeneous medium. Inaddition, selection of one or more flavoring adjuvants as well as thequantities thereof will depend upon the precise organoleptic characterdesired in the finished product. Thus, in the case of flavoringcompositions,

ingredient selection will vary in accordance with the foodstuff to whichthe flavor and aroma are to be imparted. ln contradistinction, in thepreparation of solid products, e.g., simulated foodstuffs, ingredientscapable of providing normally solid compositions should be selected suchas various cellulose derivatives.

As will be appreciated by those skilled in the art, the amount of4-(2,6,6-trimethyll ,3-cyclohexadienl -yl)- 2-butanol and/or4-(6,6-dimethyl-2-methylene-3- cyclohexen-l-yl)-2-butanol and/oracetates thereof employed in a particular instance can vary over arelatively wide range whereby to its desired organoleptic effects havingreference to the nature of the product are achieved. All parts'andpercentages given herein are byweight unless otherwise specified. Thus,correspondingly greater amounts would be necessary in those instanceswherein the .ultimate food composition to be flavored is relativelybland to the taste, whereas relatively minor quantities may suffice forpurposes of enhancing the composition merely deficient in natural flavoror aroma. Thus, the primary requirement is that the amount selected tobe effective, i.e., sufficient to alter the organoleptic characteristicsof the parent composition, whether foodstuff per se or flavoringcomposition. Thus, the useof insufficient quantities of 4-(2,6,6-trimethyll ,3-cyclohexadienl -yl)-2-butanoldimethyl-2-methylene-3-cyclohexen-l -yl)-b Z-butanol and/or acetatesthereof ranging from a small but effective amount, e.g., 0.02 parts permillion up to about 50 parts per million by weight based on totalcomposition are suitable. Concentrations in excess of the maximumquantity stated are not normally recommended since they fail to providecommensurate enhancement of organoleptic properties. In those caseswherein the 4- (2,6,6-trimethyl-l ,3-cyclohexadienl-yl)-2-butanol and/or4-(6,6-dimethyl-2-methylene-3-cyclohexen-lyl)-2-butanol and/or acetatesthereof is added to the foodstuff as an integral component of theflavoring composition, it is, of course, essential that the totalquantity of flavoring composition employed be sufficient to yield aneffective 4 (2,6,6-trimethyl-1,3- cyclohexadienl -yl)-2butanol and/or4-(6,6-dimethyl- 2-methylene-3-cyclohexenl -yl)-2-butanol and/oracetates thereof concentration in the foodstuff product.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain t-(2,6,6- trimethyll ,3-cyclohexadienl-yl)-2-butanol and/or 4 (6,6-dimethyl-2-methylene-3-cyclohexen l -yl)-2- butanol and/or acetates thereof in concentrations ranging fromabout 0.02% up to about by weight based on a total weight of saidflavoring composition.

The compositions described herein can be prepared according toconventional techniques well known as typified by cake batters andvegetable juices and can be formulated by merely admixing the involvedingredients within the proportions stated in a suitable blender toobtain the desired consistency, homogeneity of dis- ,persion, etc.Alternatively, flavoring compositions in 'the form of particulate solidscan be conveniently prepared by admixing the 4-(2,6,6-trimethyl-l,3-cyclohexadienl -yl)-2-butanol and/or 4-(6,6-dimethyl- 12-methylene-3-cyclohexen-1-yl)-2-butanol and/or acetates thereof withfor example gum arabic, gum tragacanth, carrageenan and the like andthereafter spraydrying the resultant mixture whereby to obtain theparticular solid product. Pre-prepared flavor mixes in powder form,e.g., a red currant mix or a fruit flavored powder obtained by mixingdried solid components, e.g., starch, sugar and the like and4-(2,6,6-trimethyl-l,3- cyclohexadienl -yl)-2-butanol and/0r4-(6,6-dimethyl- Z-methylenecyclohexen-l-yl)-2-butanol and/or acetatesthereof in a dry blender until the requisite degree.

of unifomity is achieved.

It is presently preferred to combine the 4-(2,6,6- and/or juvants:

Vanillin Ethyl Caproate Citral Amyl Butyrate Ethyl Butyrate EthylAcetate Amyl Acetate Cinnamyl Aldehyde Maltol Acetic Acid Ethyl MethylPhenyl Glycidate Benzyl Acetate Methyl Cinnamate Methyl AnthranilateMethyl Heptinyl Carbonate Methyl Salicylate Beta lonone GammaUndecalactone Diacetyl Anethol lsobutyl Acetate Alpha lonone p-HydroxyBenzyl Acetone Dimethyl Sulfide Acetaldehyde 4-(2,6,6-trimethyl-l,3-cyclohexadienl -yl)-2- butanol and/or 4-(6,6-dimethyl-2-methylene-3-cyclohexen-l-yl)-2-butanol and an auxiliary perfume ingredientincluding, for example, alcohols, aldehydes, nitriles, esters, cyclicesters and natural essential oils may be admixed so that the combinedodors of the individual components produce a pleasant or desiredfragrance. Such perfume compositions usually contain (a) the main noteor the bouquet or foundation stone of the composition; (b) modifierswhich round off and accompany the main note; (c) fixatives which includeodorous substances which lend a particular note to the perfumethroughout all stages of evaporation and substances which retardevaporation; and (d) topnotes which are usually low boiling freshsmelling materials.

In perfume compositions, the individual component will contribute itsparticular olfactory characteristics but the over-all effect of theperfume composition will be the sum of the effects of each of theingredients. Thus, 4-(2,6,6-trimethyll ,3-cyclohexadienl -y] )-2-butanol and/or 4-(6,6-dimethyl-2-methylene-3- cyclohexen-l-yl)-2-butanoland/or 4-(2,6,6-trimethyll,3-cyclohexadien-l-yl)-2-butyl acetate and/or4-(6,6- dimethyl-Z-methylene-3-cyclohexenl -yl )-2-butyl acetate can beused to alter the aroma characteristics of a perfume composition, forexample, by utilizing or moderating the olfactory reaction contributedby another ingredient in the composition.

The amount of the 4-(2,6,6-trimethyl-l,3- cyclohexadienl -yl)-2-butanoland/or 4-(6,6-dimethyl- 2-methylene-3-cyclohexenl -yl )-2-butanol and/or4- (2,6,6-trimethyll ,3-cyclohexadienl -yl-2-butyl acetate and/ or4-(6,6-dimethyl-2-methylene-3- cyclohexen-1-yl)-2-hutyl acetate of ourinvention which will be effective in perfume compositions depend on manyfactors including the other ingredients, their amounts and the effectswhich are desired. It has b m nd that perfume compositions containing asU Q as 010590 or 4-(2,6,6-trimethyl-l ,3- cyclohexadienl -yl )-2-butanoland/or 4-( 6,6-dimethyl- Z-mettlylene-3 cyclohexen-l-yl)-2-butanoland/or 4- (2,6,6-trimethyll ,3-cyclohexadienl -yl )-2-butyl acetateand/or 4-( 6,6-dimethyl-2-methylenecyclohexen-l yl)-2-butyl acetate oreven less can be used to impart a floral, seashore, clary sage, orrisytype scent odo'r to soaps, cosmetics and other products. The amountemployed can range up to 80% of the fragrance components and will dependon considerations of cost, nature of the end product, the effect desiredon the finished product and the particular fragrance sought.

4-( 2,6,6-trimethyl-l ,3-cyclohexadienl-yl)-2- butanol and/or4-(6,6-dimethyl-2-methylene-3- cyclohexen-l-yl)-2-butanol and/or4-(2,6,6-trimethyll,3-cyclohexadien-l-yl)-2-butyl acetate and/or 4-(6,6-dimethyl-2-methylene-3-cyclohexenl -yl)-2-butyl acetate are useful inperfume compositions as olfactory components in detergents and soaps;space odorants and deodorants; perfumes; colognes', toilet water; bathpreparations such as bath oils and bath solids; hair preparations suchas lacquers, brilliantines, pomades and shampoo; cosmetic preparationssuch as creams, deodorants, hand lotions and sunscreens; powders such astalcs, dusting powders, face powders and the like. When used as anolfactory component of a perfumed article as little as 100 parts permillion of the 4-(2,6,6- trimethyl-l ,3-cyclohexadien-l-yl)-2-butanoland/or 4- (6,6-dimethyl-2-methylene-3-cyclohexenl -yl )-2- butanoland/or 4-(2,6,6-trimethyl-1,3-cyclohexadienl-yl)-2-butyl acetate and/or4-(6,6-dimethyl-2- methylene-B-cyclohexen-l-yl)-2-butyl acetate willsuffice to impart a low keyed floral, seashore, clary sage, orrisycharacter which is one of the key odor characteristics of mimosa andorris perfume formulations. Generally, no more than 0.5% of4-(2,6,6-trimethyl- 1,3-cyclohexadienl -yl)-2-butanol and/or 4-( 6,6-dimethyl-2-methylene-3-cyclohexenl -yl)-2-butanol and/or4-(2,6,6-trimethyll ,3-cyclohexadienl -yl)-2- butyl acetate and/or4-(6,6-dimethyl-2-methylene-3- cyclohexen-1-yl)-2-butyl acetate based onthe ultimate end product is required in the perfume composition.

In addition, the perfume composition or fragrance cmposition of thisinvention contains a vehicle or carrier for the 4-(2,6,6-trimethyl-l,3-cyclohexadien-l-yl)- 2-butanol and/or 4-(6,6-dimethyl-2-methylene-3-cyclohexenl-yl)-2-butanol and/or4-(2,6,6-trimethyll,3-cyclohexadien-1-yl,)-2-butyl acetate and/or4-(6,6-

' dimethyl-2methylene-3-cyclohexen-l-yl)-2-butyl acetate. The vehiclecan be a liquid such as an alcohol, a non-toxic alcohol, a non-toxicglycol or the like. The carrier can also be an absorbent solid such as agum (e. g., gum arabic) or components for encapsulating the composition(such as gelatine).

It will thus be apparent that 4-(2,6,6-trimethyl-l,3- cyclohexadienl-yl)-2-butanol and/or 4-(6,6-dimethyl-2-methylene-3-cyclohexen-l-yl)-2-butanol and/or 4- (2,6,6-trimethyl- 1,3-cyclohexadienl -yl )-2-butyl acetate and/or 4-(6,6-dimethyl-2-methylene-3- cyclohexen-1-yl)-2-butyl acetate can beutilized to alter the sensory properties, particularly organolepticproperties such as flavor and/or fragrances of a wide variety ofconsumable materials.

In making the perfumes using the materials produced by the instantinvention, such materials can be combined with auxiliary perfumeadjuvants including one or more of many types of odor materials such asbergamot oil, vetiver oil, patchouli oil, sandalwood oil, oakmoss andfloral musk. The materials produced according to this invention can alsobe combined with a customary perfume auxiliary adjuvants such as natural12 oils, synthetic oils, ald'ehydes, letones, carboxylic acid esters,aryl alcohols, alkanols, lactones, saturated hydrocarbons, unsaturatedhydrocarbons, fixatives, solvents, dispersants, surface active agents,aerosol propellants and the like.

The following examples serve to illustrate embodiments of our inventionas it is now preferred to practice it. It will be understood that theseexamples are illustrative, and the invention is to be consideredrestrictive thereto only as indicated in the appended claims.

EXAMPLE 1 Preparation of Dihydro-a-lonol From Dihydro-a-lonone Reaction:m 0

l Heat LlAlHq Diethy ether One liter of diethyl ether is added to a 3liter reaction flask equipped with reflux condenser, stirrer,thermometer, nitrogen purge, additional funnel and heating mantle. 1OGrams of lithium aluminum hydride is then added slowly to the diethylether. Grams of dihydro-a-ionone in 400 ml diethyl ether is then addedto the lithium aluminum hydride-diethyl ether mass over a period of 1.5hours. The rate of addition is adjusted to promote and continuerefluxing. After the addition of other dihydro-a-ionone is complete, thereaction mass is refluxed using heat provided by a heating mantle. Thereaction mass is then cooled to 5C and the ex- EXAMPLE ll Preparation ofDihydro-a-lonol Acetate To a 1 liter reaction flask equipped with refluxcondenser, stirrer and heating mantle is added 100 gm. of thedihydro-a-ionol produced according to the process of Example I (0.56moles), 171 gm. of acetic anhydride (1.68 moles) and 35.0 gm. of sodiumacetate (0.25 moles). The mixture is then refluxed for 3 hours, and thencooled and 200 ml of water is added to the reaction mass. The reactionmass is warmed on a steam bath for a period of 0.5 hours and then cooledto room temperature. After cooling, the reaction mass is extracted withthree 100 ml portions of diethyl ether. The

diethyl ether extracts are combined and washed as follows:

i. Five 50 ml portions of 5% aqueous sodium carbonate solution; and ii.Two 100 ml portions of saturated NaCl solution; The ether extracts arethen dried over anhydrous mag nesium sulfate, and evaporated leaving 121gm. of residue, as ester having the structure:

EXAMPLE Ill Preparation of Dehydrodihydroionol Acetate From DihydroionolAcetate Reactio:

To a 2 liter reaction flask equipped with reflux condenser, thermometer,dry ice bath, addition funnel and nitrogen purge the following materialsare added:

(i) Dihydro-wionol prepared 120.0 gm.

according to the process (0.5 moles) of Example ll (ii) Chloroform 500ml (iii) Quinoline gm.

(0.5 moles) The resulting mixture is cooled to 5C and gm of bromine (0.5moles) in 125 ml of chloroform is added to the reaction mass over aperiod of two hours, while maintaining the temperature thereof in therange of 05C. After bromine addition, the reaction mass is stirred for 1hour at 5C and then allowed to warm up to room temperature. Thechloroform solvent is then removed at reduced pressure and the resultingresidue is heated using a steam bath for 3 hours, with N,Ndimethylaniline. The reaction mass is then cooled and 30 ml pyridine isadded. The reaction mass is then heated for a period of 30 minutes usingthe steam bath.

The resulting mixture is cooled and then added to a mixture of 600 mln-pentane and 600 ml 5N hydrochloric acid. The resulting mixture nowexists in two phases; an aqueous phase and an organic phase. The aqueousphase is extracted with three ml portions of npentane. The pentaneportions are combined with the organic phase and the resulting materialis washed as follows:

i. Twice with 5N hydrochloric acid The weight ratio of cyclohexadienederivative: methylene cyclohexene derivative is 65:18. This material hasa woody, fruity, leathery, ionone, seashore, fatty aroma with a slightmusky nuance.

EXAMPLE IV I Saponification of Dehydrodihydroionol Acetate to FormDehydrodihydroionol Reaction:

1 6 The following materials are added to a 2 liter flask equipped withstirrer and thermometer:

Dehydrodihydroionol acetate 64.9 g (produced according to the process ofExample lll) Potassium Hydroxide 24.0 g Ethyl Alcohol 600 ml Theresulting mixture is stirred for a period of 15 hours and thenneutralized with 80 ml of 5N hydrochloric acid. The ethyl alcohol isremoved under reduced pressure at 50C and the reaction mass is thendiluted with 200 ml of diethyl ether. The reaction mass is then washedwith two ml portions of saturated sodium chloride solution, after whichthe ether is evaporated yielding a 51.2 g of crude product. The crudeproduct is distilled on a microvigreaux column at 8990C and a pressureof 0.71 mm Hg pressure to yield a mixture of compounds having thestructures:'

These structures are confirmed by GLC, mass spectral and IR analyses.The weight ratio of cyclohexadiene derivativezmethylene cyclohexenederivative is 65:18. The mixture is separable by means of GLCseparation. The mixture as well as the two major individual componentsthereof have a leathery, green, seashore, orris, mimosa, clary sagearoma with a slightly musky nuance.

EXAMPLE V Orris Absolute Formulation The following formulation isprepared:

Ingredients Parts by Weight Dehydrodihydroionol prepared by 600 theprocess of Example IV p-t amyl cyclohexanone 50. Methyl ionone 75Dibutyl sulfide l Z-Nonenal 2 Ionone l Diethyl phthalate 262 Thedehydrodihydroionol produced by the process of Example IV imparts themain, deep, waxy, floral body of this orris absolute composition.

EXAMPLE VI Orris Absolute Formulation The following formulation isprepared:

Ingredients Parts by Weight Dehydrodihydroionol acetate 600 prepared bythe process of Example III p-t-amyl cyclohexanone 50 Methyl Ionone 75Dibutyl sulfide l 2-Nonenal 2 Diethyl phthalate 262 Ionone Thedehydrodihydroionol acetate produced by the process of Example IIIimparts the main, deep, waxy, floral body of this orris absolutecomposition.

EXAMPLE v11 Perfume Formulation The following mixture is preparedz The4-( 2,6,6-trimethyll ,3-cyclohexadienl -y] )-2- butanol imparts to thisformulation a low keyed floral, I

seashore, clary sage, orrisy character which are included in the keyodor characteristics of this type of aroma.

EXAMPLE VIII Preparation of Soap Composition One hundred grams of soapchips are mixed with one gram of the perfume composition of Example VIIuntil a substantially homongeneous composition is obtained. The perfumesoap composition exhibits a floral, seashore, clary sage, orrisycharacteristic.

EXAMPLE IX Preparation of a Detergent Composition A total of 100 gramsof a detergent powder is mixed with 0.15 grams of the perfumecomposition of Example VII until a substantially homogeneouoscomposition is prepared. This composition exhibits a floral, seashore,clary sage, orrisy fragrance.

EXAMPLE X Preparation of a Cosmetic Powder Composition A cosmetic powderis prepared by mixing in a ball mill 100 grams of talcum powder with0.25 grams of 4 (2,6,6-trimethyll ,3-cyclohexadienl -yl)-2-butanol. Ithas an excellent clary sage, orris, mimosa, seashore aroma.

EXAMPLE Xl Perfumed Liquid Detergent Concentrated liquid detergent witha rich mimosa character are obtained containing 0.10%, 0.15% and 0.20%of 4-(2,6,6-trimethyl-1,3-cyclohexadien-l-yl)-2- butanol. They areprepared by adding and homogeneously mixing the appropriate quantity of4-(2,6,6- trimethyl-l,3-cyclohexadien-l-yl)-2-butanol in the liquiddetergent. The'detergents all possess a clary sage, orris, mimosa,seashore fragrance, the intensity increasing with greater concentrationsof 4-(2,6,6- trimethyl-l ,3-cyclohexadien-l -yl)-2-butanol.

EXAMPLE XII Cologne 4-(2,6,6-Trimethyl-l ,3-cyclohexadienl -yl)-2-butanol is incorporated in a cologne at a concentration of 2.5% inaqueous ethanol; and into a handkerchief perfume at a concentration of5% (in aqueous ethanol). A distinct and definite clary sage, orris,mimosa, seashore fragrance is imparted to the cologne and to thehandkerchief perfume.

EXAMPLE XIII The composition of Example V is incorporated in a cologneat a concentration of 2.5% in 85% aqueous ethanol; and into ahandkerchief perfume at a concentration of 20% (in 95% aqueous ethanol).The composition of Example V affords a distinct and definite strongorris fragrance to that handkerchief perfume and cologne.

EXAMPLE XlV Flavor Formulation The following mixture is prepared:

Ingredients Parts by Weight Vanillin 2O Allyl Caproate 10 Citral 2O AmylButyrate 35 Orange Oil 45 Ethyl Butyrate 75 Ethyl Acetate 185 AmylAcetate 185 Lemon Oil 400 4-( 2,6,6-Trimethyll ,3-cyclohexadienl -yl)-2-butanol was added to 975 grams of the above mixture which was thencalled Test Composition. A control composition was prepared by adding 25grams of additional lemon oil to 975 grams of the above mixture.

The test and control compositions were added to the food productsdescribed hereinafter and the proportions shown for 100 kilograms ofmaterial to be flavored:

Cake 20 grams Pudding 5-10 grams Cooked sugar 15-20 grams Cooked sugar100 ml of sugar syrup (prepared by dissolving l kilogram of sucrose in600 ml of water) and 20 grams of glucose were mixed together and slowlyheated to 145 C. The flavor was added and the mass allowed to cool andharden.

Pudding To 500 ml of warmed milk were added with stirring a mixture of60 grams sucrose and 3 grams of pectin. The mixture was boiled for a fewseconds and the flavor was added. The mixture was allowed to cool.

Cake The following ingredients were mixed together:

Vegetable margarine 100 grams Sodium Chloride 1.5 grams Sucrose 100grams Eggs 2 Flour 100 grams The flavor was added and the mass wascooked for 40 minutes at 180C. The finished foodstuff samples weretested by a panel of trained persons who had to express their viewsabout the flavor of the samples. All members of the panel declared withno hesitation that the test samples had a more distinguished fruity andwoody note than the control samples and at the same time a red-berrycharacter.

EXAMPLE XV Raspberry Flavor The following mixture is prepared:

Ingredient Parts by Weight Para-hydroxy benzyl acetone 5 -ContinuedIngredient Parts by Weight Vanillin 2 Maltol 3 Alpha-lonone 1% solutionin 15 propylene glycol) Isobutyl Acetate l5 Ethyl Butyrate 5 EthylAcetate 5 Dimethyl Sulfide 10% solution in 5 propylene glycol) Aceticacid 15 Acetaldehyde 20 Propylene Glycol 910 A 65:18 wt/Wt mixture of4-(2,6,6-trimethyl-l ,3-cyclohexadien-1-yl)-2-butanol:4-(6,6-trimethyl-2-methylene-3-cyclohexen-l-yl)2-butanol (produced by the process ofExample IV) is added to the above mixture at the rate of 0.1%. A flavorformulation with this mixture of butanol derivatives is then comparedwith the same flavor formulation without the mixture of butanolderivatives at the rate of 0.01% in water ppm) by a bench panel. Theflavor formulation containing the mixture of butanol derivatives has astrong delicate raspberry aroma and a cooked jam-like raspberry tastewhich characteristics are not reproduced by the flavor formulation whichdoes not contain the mixture of butanol derivatives.

EXAMPLE XVI Raspberry Flavor The following mixture is prepared:

lngredient Parts by Weight Para-hydroxy benzyl acetone 5 Vanillin 2Maltol 3 Alpha-Ionone 1% solution in 15 propylene glycol) lsobutylacetate 15 Ethyl Butyrate 5 Ethyl Acetate 5 Dimethyl Sulfide 10%solution in 5 propylene glycol) Acetic acid 15 Acetaldehyde 20 PropyleneGlycol 910 EXAMPLE XVll Raspberry Flavor The following mixture isprepared:

Ingredient Parts by Weight Para-hydroxy bcnzyl acetone 5 Vanillin 2Maltol 3 Linalool -Continued -Continued Ingredient I Parts by WeightIngredients Parts by Weight Alpha-ionone 1% solution in 154(4-methyl4hydroxyamyl)-A"-cyclo- 20.0 propylene glycol)hexane-carboxyaldehyde lsobutyl acetate 1 15 5 Benzyl Alcohol 90.0 Ethylbutyrate 5 Benzyl Acetate 150.0 Ethyl Acetate 54-(2,6,6-trimethyl-1,3-cyclohexadien- 3.0 Dimethyl Sulfide solution in 51-yl)2-butanol propylene glycol) Acetic acid Acetaldehyde PropyleneGlycol 910 10 The 4-(2,6,6-trimethyl-1,3-cyclohexadlen-1-yl)-2- butanolimparts to the above floral type formulation, a u clary sage, orris,mimosa, seashore aroma. 4-( 2,6,6-tr1methyl-1 ,3-cyclohexad1enl -yl)-2-butanol is added to the above mixture at the rate of 0.1%. A fla-EXAMPLE XX vor formulation with this butanol derivative is then 15perfume Formulation compared with the same flavor formulation withoutthis butanol derivative at the rate of 0.01% in water The followmgmlxture prepared (100 ppm) by a bench panel. The flavor formulationcontaining the butanol derivative has a strong delicate ingredients Pansby weight raspberry aroma and a cooked am-like raspberry taste 20 whichcharacteristics are not re roduced b the flavor Idol f I h d p h b y l dI Methyl Anthranilate 2.0 ormu atron WhlC oes not contain t e utanoerivamHePtYl cyclopenmmm 30 tive, Grisalva (produced by the 50% sulfuric4.0 treatment of 3-ethyl-l-(2,2, 6-trimethylcyclohexen-5-yl- EXAMPLEXVIII l)-hexen-3ol-6) 6,7-Dihydro1,1,2,3,3.penta- 2.0 The followingmixture 1s prepared. methYMFGH) indanone (produced according to thepreparation of A of Swiss Ingredients Parts by Weight Patent Oil ofBitter Orange 50 Natural Raspberry Concentrate 2V2% y Juice6,7,8-hexahydro-1l-l-benz-( f )-mdene water 5 Terpineol Coeur 10.0 S 1 B21 17 Nerolidol 10.0 ugar syrup 2 mime) 0 2-t-butyl-cyclohexany1 acetate20.0 Linalyl Acetate 90.0 Linalool 1 10.0 The seedy note of thisraspberry juice is imparted in 35 y y y y y h b f f th f u whexene-carboxaldehyde increasing strengt y a mon 0 e1 er 0 e o o BenZylAlcohol 900 ing materials at the rate of from 0.02 ppm up to 1.0 BenzylAcetate 150.0 4-(6,6-dimethyl-2-methylenc-3-cyclo- 3.0 hexenl -yl)-2-butano1 4-( 2,6,6-tr1methyl-1 ,3-cyclohexad1enl -yl)-2- butanol 4O yy y -y The 4-(6,6-dimethyl-2-methylene-3-cyclohexen-1- butanolyl)-2-butanol impartslto the above floral type formula- 65=18weightlweight mlxtule 0f y tion, a clary sage, orris, mimosa, seashorearoma.

l ,3-cyclohexadien-l -yl)2-butanol and 4-( 6,6dimethyl-2-methylene-3-cyclohexen-l-yl)-2-' EXAMPLE XXI butanol PerfumeFormulation EXAMPLE XIX The following mixture is prepared:

Perfume Formulation 5O The following mixture is prepared: lngredwm-SParts by wei ht lndol 2.0 Methyl Anthranilate 20 Ingredients Parts byWcight n-Heptyl Cyclopcntanone 3.0 Grisalva (produced by the 4.0 l d l2.0 sulfuric acid treatment Methyl Anthranilatc 2.0 of 3ethyl-l-(2,2.6-n-Heptyl Cyclopcntanone 3.0 tnmethyl-cyclohcxen-S- Grisalva (produced bythe 50% surfuric 4.0 yl-1 )-hcxen 3-o1-6) acid treatment of3-ethy1-1-(2,6.6-tri- 6.7-D|hydl '0-l.l. -P y -0methyl-cyclohexcn-Syl-1)-hexcn-3-o1-6) 4-(5H) ne (produced according 6 7Dih d .1 1,2 3 3 m 2.0 to the preparation of A of SWISS methy1-4-(5H)indanone Patent 523,962) (produced according to the 011 of Bitter Orange5 preparation of A of Swiss 2-Oxa1.1,3,3-tctramethyl-2,3.5, 5.0 Patent523,962) 6.7,8-hexahydro- 1 H-bcnz(f)indene Oil of Bitter Orange 50Terpincol Coeur 101) Z-Oxa- 1 1 ,3,3-tetramethyl-2.3,5.6. 5.0 Nerohdol101) 7.8-hexahydro-1H-benz-(f)-indenc I 2- t-butyl-cyclohexany1 acetate20.0 Terpincol Coeur 10.0 5 Lmalyl Acetate 9() Nerolidol 10.0 Linalool 110.0 Z-t-butyl-cyclohexanyl acetate 20.0 4-( mcthyl-4-hydroxyamyl)-A-'-cyc1o- 20.0 Linalyl A tate 90.0 hexene-carboxyaldehyde 1 10.0Bcnzyl Alcohol 90.0

4-( 2,6,6-trimethyll ,3-cyclohexadienl -yl )-2- butanol and4-(6,6-dimethyl-2-methylene-3-cyclohexen-1- yl )-3-butanol The mixtureof 4-(2,6,6-trimethyl-l ,3-

cyclohexadien-l-yl)-2-butanol and 4-(6,6-dimethyl-2-methylene-3-cyclohexenl -yl)-2-butanol imparts to the above floral typeformulation a clary sage, orris, mimosa, seashore aroma.

EXAMPLE XXII Perfume Formulation The following mixture is prepared:

Ingredients Parts by Weight Methyl Acetophenone 4 Terpineol 450 PhenylEthyl Alcohol 50 Bergamot Oil 20 Methyl Heptinyl Carbonate 1 Productproduced according to the 20 process of Example III I-Ieliotropin 30Anisic Aldehyde I80 Methyl Anthranilate 5 Jasmine Absolute 30 CinnamicAlcohol 100 Cassie Absolute l0 Hydroxycitronellal 100 The productproduced by the process of Example III imparts to this formulation awoody, fruity, leathery, ionone, fatty character with a slightly muskynuance which are included in the key odor characteristics of this typeof aroma.

EXAMPLE XXIII Preparation of Soap Composition One hundred grams of soapchips are mixed with one gram of the perfume composition of Example XXIIuntil a substantially homogeneous composition is obtained. The perfumedsoap composition exhibits a woody, fruity, leathery, ionone, fattycharacter with a slightly musky nuance.

EXAMPLE XXIV Preparation of aDetergent Composition A total of 100 gramsof a detergent powder is mixed with 0.15 grams of the perfumecomposition of Example XXII until a substantially homogeneouscomposition is prepared. This composition exhibits a woody, fruity,leathery, ionone, fatty character with a slightly musky nuance.

EXAMPLE XXV Preparation of a Cosmetic Powder Composition A cosmeticpowder is prepared by mixing in a ball mill 100' grams of talcum powderwith 0.25 grams of the product produced by the process of Example III.It has an excellent woody, fruity, leathery, ionone, fatty characterwith a slightly musky nuance.

EXAMPLE XXVI Perfumed Liquid Detergent Concentrated liquid detergentwith a rich woody, fruity, leathery, ionone, fatty character areobtained containing 0.10%, 0.15% and 0.20% of the product produced bythe process of Example III. They are prepared by adding andhomogeneously mixing the appropriate quantity of the product produced bythe process of Example III in the liquid detergent. The detergents allpossess a woody, fruity, leathery, ionone, fatty character with aslightly musky nuance, the intensity increasing with greaterconcentrations of the product produced by the process of Example III.

EXAMPLE XXVII Cologne The product produced by the process of Example IIIis incorporated in a cologne at a concentration of 2.5% in 85% aqueousethanol; and into a handkerchief perfume at a concentration of 5% (in95% aqueous ethanol). A distinct and definite woody, fruity, leatherly,ionone, fatty fragrance is imparted to the cologne and to thehandkerchief perfume.

What is claimed is:

l. A process for altering the flavor of a raspberry flavored foodstuffcomprising adding to said raspberry flavored foodstuff in an amount offrom 0.02 up to 50 ppm, an oxo compound selected from the groupconsisting of 4-(2,6,6-trimethyll ,3-cyclohexadienl -yl)-2- butanol,4-(6,6-dimethyl-2-methylene-3-cyclohexen-l yl )-2-butanol, 4-(2,6,6-trimethyl-l ,3-cyclohexadienl y])-2-butyl acetate and4-(6,6-dimethyl-2-methylene-3- cyclohexenl -yl)-2-butyl acetate, andmixtures thereof.

2. The process of claim 1 wherein the oxo compound is a mixture of4-(2,6,6-trimethyl-l,3-cyclohexadien-lyl)-2-butanol and4-(6,6-dimethyl-2-methylene-3- cyclohexenl -yl )-2-butanol. I

3. The process of claim 2 wherein the ratio of 4- (2,6,6-trimethyll,3-cyclohexadienl -yl)-2-butanol to 4-(6,6-dimethyl-2-methylene-3-cyclohexenl -yl )-2- butanol is 65:18.

4. The process of claim 1 wherein the oxo compound is a mixture of4-(2,6,6-trimethyll ,3-cyclohexadien-lyl)-2-butyl acetate and4-(6,6-dimethyl-2-methylene-3- cyclohexenl -yl )-2-butyl acetate.

5. The process of claim 4 wherein the ratio of 4- (2,6,6-trimethyll,3-cyclohexadienl -yl )-2-butyl acetate to4-(6,6-dimethyl-2-methylene-3-cyclohexen-lyl)-2-butyl acetate is 65:18.

6. The process of claim 1 wherein the oxo compound is 4-(2,6,6-trimethyll ,3-cyclohexadienl -yl )-2- butanol.

7. The process of claim 1 wherein the oxo compound is 4-(6,6-dimethyl-2-methylene-3-cyclohexenl -yl )-2- butanol.

8. The process of claim 1 wherein the oxo compound acetate.

9. The process of claim 1 wherein the oxo compound is 4-(6,6-dimethyl-2-methylene-3-cyclohexenl -yl)-2- butyl acetate.

4-(2,6,6-trimethyl-l ,3-cyclohexadien-l -yl)-2-butyl

1. A PROCESS FOR ALTERING THE FLAVOR OF A RASPBERRY FLAVOURED FOODSTUFFCOMPRISING ADDING TO SAID RASPBERRY FLAVOURED FOODSTUFF IN AN AMOUNT OFFROM 0.02 UP TO 50 PPM, AN OXO COMPOUND SELECTED FROM THE GROUPCONSISTING OF 4-(2,6,6-TRIMETHYL-1.3-CYCLOHEXADIEN-1-Y1)-2-BUTANOL,4-(6,6-DIMETHYL-2METHYLENE-3-CYCLOHEXEN-1-YL-)2-BUTANOL,4-(2,6,6-TRIMETHYL1,3-CYCLOHEXADIEN-1-YL)-2BUTYL ACETATE AND4-(6,6-DIMETHYL2-METHYLENE-3-CYCLOHEXEN-1-YL)-2 BUTYL ACETATE, ANDMIXTURES THEREOF.
 2. The process of claim 1 wherein the oxo compound isa mixture of 4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butanol and4-(6, 6-dimethyl-2-methylene-3-cyclohexen-1-yl)-2-butanol.
 3. Theprocess of claim 2 wherein the ratio of4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butanol to4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-2-butanol is 65:18. 4.The process of claim 1 wherein the oxo compound is a mixture of4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butyl acetate and4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-2-butyl acetate.
 5. Theprocess of claim 4 wherein the ratio of4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butyl acetate to4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-2-butyl acetate is 65:18.6. The process of claim 1 wherein the oxo compound is4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butanol.
 7. The process ofclaim 1 wherein the oxo compound is4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-2-butanol.
 8. The processof claim 1 wherein the oxo compound is4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butyl acetate.
 9. Theprocess of claim 1 wherein the oxo compound is4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-2-butyl acetate.